CN116874953A - High-temperature-resistant corrosion-resistant PVC material - Google Patents
High-temperature-resistant corrosion-resistant PVC material Download PDFInfo
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- CN116874953A CN116874953A CN202310949068.3A CN202310949068A CN116874953A CN 116874953 A CN116874953 A CN 116874953A CN 202310949068 A CN202310949068 A CN 202310949068A CN 116874953 A CN116874953 A CN 116874953A
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 230000007797 corrosion Effects 0.000 title claims abstract description 48
- 238000005260 corrosion Methods 0.000 title claims abstract description 48
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 102
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 102
- 239000010445 mica Substances 0.000 claims abstract description 71
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 71
- 239000000843 powder Substances 0.000 claims abstract description 71
- 239000004417 polycarbonate Substances 0.000 claims abstract description 62
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 62
- 150000002009 diols Chemical class 0.000 claims abstract description 61
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 18
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QYUMESOEHIJKHV-UHFFFAOYSA-M prop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].NC(=O)C=C.CCC[N+](C)(C)C QYUMESOEHIJKHV-UHFFFAOYSA-M 0.000 claims description 7
- MRUCFNWPEGEZSP-UHFFFAOYSA-N butanoic acid;pyrrole-2,5-dione Chemical compound CCCC(O)=O.O=C1NC(=O)C=C1 MRUCFNWPEGEZSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- 230000032683 aging Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of materials, and discloses a high-temperature-resistant corrosion-resistant PVC material, which comprises the following raw materials: polyvinyl chloride, modified mica powder, functionalized polycarbonate diol, a dispersing agent, an initiator, a lubricant and a stabilizer; the invention has the advantages that: the prepared functional polycarbonate diol has excellent high temperature resistance and antibacterial performance, the quaternary ammonium group has a broad-spectrum antibacterial effect, the maleimide group contains a rigid structure, the stability, corrosion resistance and high temperature resistance of the PVC material can be improved, and the mica powder has excellent heat resistance, corrosion resistance and mechanical properties, so that the prepared PVC material has better stability, corrosion resistance and high temperature resistance, the antibacterial capability, high temperature resistance degree and mechanical properties of the PVC material are improved, and the service life of the PVC material and the service life of a product prepared from the PVC material are also prolonged.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a high-temperature-resistant corrosion-resistant PVC material.
Background
Polyvinyl chloride is a material which is low in price, various in formula and easy to process, has good electrical insulation, flame retardance and plasticity, is widely applied to the fields of cables, shoes, packaging films, pipes, daily necessities and the like, but is an amorphous polymer containing a small amount of crystal structures, carbon atoms are arranged in a zigzag manner, a short syndiotactic structure exists on a molecular chain, so that polyvinyl chloride macromolecules have the defects of thermal deformation resistance and poor ageing resistance, in the fields of cables, pipes and the like, the requirements on the high temperature resistance and the light ageing resistance of the polyvinyl chloride materials are high due to the fact that part of the polyvinyl chloride macromolecules need to be exposed to the outdoor environment for a long time, and the requirements on the corrosion resistance of the cables or pipes buried in the ground are high, so that in the field of daily necessities, the polyvinyl chloride materials are often modified in specific occasions, one of the most widely applied modification methods is to blend the polyvinyl chloride with the modified materials, and the blended polyvinyl chloride cannot greatly improve the stability but has new functions.
The patent with publication number CN110951189B discloses a polyvinyl chloride material and a preparation method thereof, and the obtained polyvinyl chloride material has high temperature resistance, cold resistance and flame retardance, can be normally used in an environment with high temperature of 125 ℃ and low temperature of minus 50 ℃, has excellent flame retardance, but has no improvement on the antibacterial property of the polyvinyl chloride material, and has the risk of precipitation of the antioxidant and the stabilizer during long-time use due to direct addition of the antioxidant and the stabilizer.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant corrosion-resistant PVC material, which solves the following technical problems: (1) The PVC material has low high temperature resistance and corrosion resistance; (2) the PVC material has poor stability and is easy to age; (3) The mechanical properties of the PVC material need to be further enhanced; (4) the PVC material is easy to grow bacteria.
The aim of the invention can be achieved by the following technical scheme:
the high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 30-80 parts of polyvinyl chloride, 3-8 parts of modified mica powder, 5-10 parts of functionalized polycarbonate diol, 1-2 parts of dispersing agent, 0.5-2 parts of initiator, 0.1-0.5 part of lubricant and 1-2 parts of stabilizer; the functionalized polycarbonate diol is prepared by sequentially reacting polycarbonate diol with maleimide butyric acid and (acrylamide propyl) trimethyl ammonium chloride; the modified mica powder is prepared by sequentially reacting mica powder with mercaptopropyl trimethoxy silane and 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidinyl ester.
Further, the dispersant is dispersant 65SH50; the initiator is azodiisobutyronitrile; the lubricant is pentaerythritol stearate; the stabilizer is zinc stearate.
Further, the preparation method of the functionalized polycarbonate diol comprises the following steps:
s1, placing polycarbonate diol in ethanol, stirring for 10-15min, introducing nitrogen, adding maleimide butyric acid, continuously stirring for 4-8h, and removing the solvent by rotary evaporation to obtain modified polycarbonate diol;
s2, placing the modified polycarbonate diol in toluene, stirring for 10-15min, adding (acrylamide propyl) trimethyl ammonium chloride and an initiator 1, introducing nitrogen, heating to 75-85 ℃ and stirring for 2-3h, and removing the solvent by rotary evaporation to obtain the functionalized polycarbonate diol.
Through the technical scheme, the hydroxyl in the polycarbonate diol structure and the carboxyl in the maleimide butyric acid structure are subjected to esterification reaction, and the maleimide group is introduced into the polycarbonate diol structure to obtain the modified polycarbonate diol, and under the action of the initiator 1, the double bond in the modified polycarbonate diol structure provides an active initiation site for (acrylamide propyl) trimethyl ammonium chloride to initiate free radical polymerization of the (acrylamide propyl) trimethyl ammonium chloride, so that the functionalized polycarbonate diol is obtained.
Further, in step S1, the average molecular weight of the polycarbonate diol is 2000.
Further, in step S2, the initiator 1 is dibenzoyl peroxide.
Further, the preparation method of the modified mica powder comprises the following steps:
SS1, placing mica powder in ethanol, performing ultrasonic dispersion for 0.5-1h, adding mercaptopropyl trimethoxy silane, heating for reaction, filtering, washing and vacuum drying to obtain a modified mica powder intermediate;
SS2, the modified mica powder intermediate is placed in N, N-dimethylformamide, dispersed for 0.5 to 1 hour by ultrasonic, 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidinyl ester and photoinitiator are added, and the weight of the mixture is 1.8 to 2.3mw/cm 2 After reacting for 0.5-1h under the irradiation of ultraviolet light, filtering, washing and vacuum drying to obtain the modified mica powder.
According to the technical scheme, hydroxyl on the surface of mica powder reacts with a silane coupling agent, active sulfhydryl is grafted on the surface of mica powder to obtain a modified mica powder intermediate, and under the action of an accelerator, the sulfhydryl on the surface of the modified mica powder intermediate is subjected to click reaction with alkenyl in a 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidyl ester structure through ultraviolet light irradiation to obtain the modified mica powder.
Further, in the step SS1, the temperature of the heating reaction is 60-70 ℃ and the time is 1-3h.
Further, in step SS2, the photoinitiator is any one of benzoin diethyl ether, benzoin isopropyl ether, and benzoin dimethyl ether.
Further, the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, modified mica powder, functionalized polycarbonate diol, a dispersing agent, an initiator, a lubricant and a stabilizer in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to be 700-800r/min, heating to 105-110 ℃, stirring for 1-2h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 160-180 ℃, the screw rotating speed to be 300-500r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
The invention has the beneficial effects that:
(1) According to the invention, the functionalized polycarbonate diol is prepared as a modified material of the PVC material, the polycarbonate diol has excellent high temperature resistance and corrosion resistance, the stability, corrosion resistance and high temperature resistance of the PVC material can be improved after the polycarbonate diol is blended with the PVC material, after modification, the quaternary ammonium group in the structure has a broad-spectrum antibacterial effect, the PVC material can be endowed with excellent antibacterial performance, the application range of the PVC material is increased, the maleimide group in the structure contains a rigid structure, the high temperature resistance and the mechanical strength of the PVC material can be well improved, and the service life of the PVC material is remarkably prolonged.
(2) According to the invention, the modified mica powder is prepared as the filler of the PVC material, imine groups on the surface of the modified mica powder can interact with active chlorine in a PVC structure, so that the dispersibility of the modified mica powder in the PVC material is remarkably improved, the modified mica powder is not easy to generate agglomeration phenomenon, the compatibility of the modified mica powder and the PVC material is improved, the modified mica powder is not easy to fall off, the service life of the PVC can be further prolonged, a hindered amine group is arranged in the structure of the modifier 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidinyl ester, free radicals generated in the photooxidation and degradation processes of the PVC can be captured, the ultraviolet resistance and stability of the PVC are improved, the mica powder is excellent in heat resistance, corrosion resistance and mechanical property, the modified mica powder is uniformly dispersed in the PVC material, the high temperature resistance, the mechanical property and the corrosion resistance of the PVC are remarkably improved, meanwhile, the modified mica powder is also excellent in ultraviolet resistance, the aging process of the PVC can be delayed, and the 2-methyl-2, 6-tetramethyl-4-piperidinyl ester can be grafted on the surface of the PVC material in a chemical bonding manner, and the ultraviolet resistance of the PVC material can be jointly improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the thermal weight loss of the mica powder, modified mica powder intermediate and modified mica powder according to example 1 of the present invention;
FIG. 2 is an infrared spectrum of a modified polycarbonate diol and a functionalized polycarbonate diol in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 30 parts of polyvinyl chloride, 3 parts of modified mica powder, 5 parts of functionalized polycarbonate diol, 1 part of dispersing agent 65SH50, 0.5 part of azodiisobutyronitrile, 0.1 part of pentaerythritol stearate and 1 part of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, modified mica powder, functionalized polycarbonate diol, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to be 700r/min, heating to 105 ℃, continuously stirring for 1h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to 160 ℃, the screw rotating speed to 300r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
The preparation method of the functionalized polycarbonate diol comprises the following steps:
s1, placing 2.8ml of polycarbonate diol into 50ml of ethanol, stirring for 10min, introducing nitrogen to deoxidize, adding 1.6g of maleimide butyric acid, continuously stirring for 4h, and removing the solvent by rotary evaporation to obtain modified polycarbonate diol;
s2, placing 2.5ml of modified polycarbonate diol into 80ml of toluene, stirring for 10-15min, adding 2ml of (acrylamide propyl) trimethyl ammonium chloride and 0.2g of dibenzoyl peroxide, introducing nitrogen, heating to 75 ℃, stirring for 2h, and removing the solvent by rotary evaporation to obtain the functionalized polycarbonate diol.
Characterization of modified polycarbonate diol and functionalized polycarbonate diol by infrared spectroscopic test, the test results are shown in FIG. 2, and it can be seen from FIG. 2 that the infrared spectrum of the modified polycarbonate diol is 3060cm in the infrared spectrum -1 An absorption peak of a carbon-carbon hydrogen bond in a carbon-carbon double bond appears at 1716cm -1 Is characterized by an absorption peak of carbon-oxygen double bond in ester group of 3021cm -1 The absorption peak of the carbon-hydrogen bond in the benzene ring is shown; in the infrared spectrum of the functionalized polycarbonate diol, the absorption peak of the carbon-hydrogen bond in the carbon-carbon double bond can be seen to disappear, 1718cm -1 The absorption peak of the carbon-oxygen double bond in the ester group at the position becomes stronger and 3023cm -1 The absorption peak of the carbon-hydrogen bond in the benzene ring becomes stronger at 3385cm -1 The absorbance peak of the imine group was observed at 3014cm -1 With 1450cm -1 The absorption peak of the quaternary ammonium salt appears.
The preparation method of the modified mica powder comprises the following steps:
s1, placing 2.5g of mica powder into 80ml of ethanol, performing ultrasonic dispersion for 0.5h, adding 2ml of mercaptopropyl trimethoxy silane, heating to 60 ℃ for reaction for 1h, filtering, washing and vacuum drying to obtain a modified mica powder intermediate;
s2, placing 2g of modified mica powder intermediate in 50ml of N, N-dimethylformamide, dispersing for 0.5-1h by ultrasonic, adding 1.5g of 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidyl ester and 0.1g of benzoin diethyl ether, and adding the mixture into the mixture at the concentration of 1.8mw/cm 2 After reacting for 0.5h under the irradiation of ultraviolet light, filtering, washing and vacuum drying to obtain the modified mica powder.
By carrying out thermal gravimetric analysis on the mica powder, the modified mica powder intermediate and the modified mica powder by a thermogravimetric analysis method, as can be seen from fig. 1, the final mass retention rate of the mica powder is 97.3% at a high temperature of 800 ℃, the loss part is caused by thermal decomposition of crystal water in the structure, the final mass retention rate of the modified mica powder intermediate is 61.7%, the loss part is caused by thermal decomposition of a silane coupling agent grafted on the surface of the modified mica powder intermediate, the final mass retention rate of the modified mica powder is 30.4%, and the loss part is caused by thermal decomposition of an organic matter grafted on the surface of the modified mica powder.
Example 2
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride, 5 parts of modified mica powder, 8 parts of functionalized polycarbonate diol, 1.5 parts of dispersing agent 65SH50, 1 part of azodiisobutyronitrile, 0.3 part of pentaerythritol stearate and 1.5 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, modified mica powder, functionalized polycarbonate diol, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 750r/min, heating to 108 ℃, continuously stirring for 1.5h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 170 ℃, the rotating speed of the screw to be 400r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Wherein, the preparation method of the modified mica powder and the functionalized polycarbonate diol is the same as that of the example 1.
Example 3
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 8 parts of modified mica powder, 10 parts of functionalized polycarbonate diol, 2 parts of dispersing agent 65SH50, 2 parts of azodiisobutyronitrile, 0.5 part of pentaerythritol stearate and 2 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, modified mica powder, functionalized polycarbonate diol, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 800r/min, heating to 110 ℃, continuously stirring for 2 hours, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 180 ℃, the rotating speed of the screw to be 500r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Wherein, the preparation method of the modified mica powder and the functionalized polycarbonate diol is the same as that of the example 1.
Comparative example 1
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride, 8 parts of functionalized polycarbonate diol, 1.5 parts of dispersing agent 65SH50, 1 part of azodiisobutyronitrile, 0.3 part of pentaerythritol stearate and 1.5 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, functionalized polycarbonate diol, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 750r/min, heating to 108 ℃, continuously stirring for 1.5h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 170 ℃, the rotating speed of the screw to be 400r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Wherein the preparation method of the functionalized polycarbonate diol is the same as in example 1.
Comparative example 2
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride, 5 parts of modified mica powder, 1.5 parts of dispersing agent 65SH50, 1 part of azodiisobutyronitrile, 0.3 part of pentaerythritol stearate and 1.5 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, modified mica powder, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 750r/min, heating to 108 ℃, continuously stirring for 1.5h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 170 ℃, the rotating speed of the screw to be 400r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Wherein the preparation method of the modified mica powder is the same as in example 1.
Comparative example 3
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride, 1.5 parts of dispersing agent 65SH50, 1 part of azodiisobutyronitrile, 0.3 part of pentaerythritol stearate and 1.5 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 750r/min, heating to 108 ℃, continuously stirring for 1.5h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 170 ℃, the rotating speed of the screw to be 400r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Comparative example 4
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride, 5 parts of mica powder, 8 parts of functionalized polycarbonate diol, 1.5 parts of dispersing agent 65SH50, 1 part of azodiisobutyronitrile, 0.3 part of pentaerythritol stearate and 1.5 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, mica powder, functionalized polycarbonate diol, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 750r/min, heating to 108 ℃, continuously stirring for 1.5h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 170 ℃, the rotating speed of the screw to be 400r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Wherein the preparation method of the functionalized polycarbonate diol is the same as in example 1.
Comparative example 5
The high-temperature-resistant corrosion-resistant PVC material comprises the following raw materials in parts by weight: 60 parts of polyvinyl chloride, 5 parts of modified mica powder, 8 parts of polycarbonate diol, 1.5 parts of dispersing agent 65SH50, 1 part of azodiisobutyronitrile, 0.3 part of pentaerythritol stearate and 1.5 parts of zinc stearate;
the preparation method of the PVC material comprises the following steps:
adding polyvinyl chloride, modified mica powder, polycarbonate diol, a dispersing agent 65SH50, azodiisobutyronitrile, pentaerythritol stearate and zinc stearate in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to 750r/min, heating to 108 ℃, continuously stirring for 1.5h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 170 ℃, the rotating speed of the screw to be 400r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
Wherein the preparation method of the modified mica powder is the same as in example 1.
And (3) performance detection:
the PVC materials prepared in examples 1 to 3, comparative examples 1 to 5 were subjected to a tabletting treatment, cut into standard-compliant samples, and the samples were tested for tensile strength at a tensile rate of 50mm/min with reference to GB/T1040.2-2022, and were placed in an ultraviolet aging oven at an ultraviolet wavelength of 313nm with an irradiance of 0.72/m 2 The sample after 24 hours of radiation is subjected to tensile strength test; referring to GB/T1633-2000, testing the Vicat softening temperature of the sample, and judging the high temperature resistance of the sample; by placing the sample in a concentrationThe corrosion resistance of the sample is tested by counting the weightlessness condition in a hydrochloric acid solution with the temperature of 1mol/L and a sodium hydroxide solution with the temperature of 1mol/L for 12 hours; the antibacterial property of the sample is detected by adopting the following method: 1ml was concentrated to 10 -5 The method comprises the steps of respectively dripping CFU/ml escherichia coli bacterial liquid onto the surface of a sample after sterilization treatment, culturing for 8 hours at 37 ℃, transferring 20 mu L of the cultured bacterial liquid, uniformly coating the bacterial liquid on a solid culture medium, culturing for 24 hours at 37 ℃, counting the colony number on the culture medium, simultaneously performing a blank experiment, and calculating the antibacterial rate by using the following formula:
wherein A is the number of colonies in a blank experiment; b is the number of bacterial colonies in the sample group experiment; the test results are shown in the following table:
as is clear from the above table, the samples prepared in examples 1 to 3 are excellent in high temperature resistance, corrosion resistance, antibacterial property, aging resistance and mechanical property, the samples prepared in comparative example 1 are not added with modified mica powder, and are added with functional polycarbonate diol, the antibacterial property is excellent, the high temperature resistance, corrosion resistance and mechanical strength are moderate, the samples prepared in comparative example 2 are not added with functional polycarbonate diol, modified mica powder is added, the ageing resistance is excellent, the high temperature resistance, corrosion resistance and mechanical property are moderate, the antibacterial effect is poor, the samples prepared in comparative example 3 are not added with modified mica powder and functional polycarbonate diol, the high temperature resistance, corrosion resistance, aging resistance and mechanical property are poor, the samples prepared in comparative example 4 are added with unmodified mica powder and functional polycarbonate diol, the high temperature resistance, corrosion resistance, mechanical strength and mechanical property are high, but after ultraviolet radiation is obviously reduced, the ageing resistance is poor, the compatibility of the unmodified mica powder and the mechanical property is poor, the high temperature resistance is poor, the mechanical property is greatly reduced, and the ageing resistance is poor, compared with the conventional polycarbonate, and the ultraviolet radiation resistance is greatly reduced, the ageing resistance is poor, and the mechanical property is greatly reduced, and the ageing resistance is greatly improved, and the mechanical resistance is greatly improved.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar alternatives may be made by those skilled in the art, without departing from the scope of the invention as defined by the principles of the invention.
Claims (9)
1. The high-temperature-resistant corrosion-resistant PVC material is characterized by comprising the following raw materials in parts by weight: 30-80 parts of polyvinyl chloride, 3-8 parts of modified mica powder, 5-10 parts of functionalized polycarbonate diol, 1-2 parts of dispersing agent, 0.5-2 parts of initiator, 0.1-0.5 part of lubricant and 1-2 parts of stabilizer; the functionalized polycarbonate diol is prepared by sequentially reacting polycarbonate diol with maleimide butyric acid and (acrylamide propyl) trimethyl ammonium chloride; the modified mica powder is prepared by sequentially reacting mica powder with mercaptopropyl trimethoxy silane and 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidinyl ester.
2. The high temperature and corrosion resistant PVC material according to claim 1, wherein the dispersant is dispersant 65SH50; the initiator is azodiisobutyronitrile; the lubricant is pentaerythritol stearate; the stabilizer is zinc stearate.
3. The high temperature and corrosion resistant PVC material according to claim 1, wherein the functionalized polycarbonate diol is prepared by the following steps:
s1, placing polycarbonate diol in ethanol, stirring for 10-15min, introducing nitrogen, adding maleimide butyric acid, continuously stirring for 4-8h, and removing the solvent by rotary evaporation to obtain modified polycarbonate diol;
s2, placing the modified polycarbonate diol in toluene, stirring for 10-15min, adding (acrylamide propyl) trimethyl ammonium chloride and an initiator 1, introducing nitrogen, heating to 75-85 ℃ and stirring for 2-3h, and removing the solvent by rotary evaporation to obtain the functionalized polycarbonate diol.
4. A high temperature and corrosion resistant PVC material according to claim 3, wherein in step S1 the average molecular weight of the polycarbonate diol is 2000.
5. A high temperature and corrosion resistant PVC material according to claim 3, wherein in step S2, the initiator 1 is dibenzoyl peroxide.
6. The high-temperature-resistant corrosion-resistant PVC material according to claim 1, wherein the preparation method of the modified mica powder is as follows:
SS1, placing mica powder in ethanol, performing ultrasonic dispersion for 0.5-1h, adding mercaptopropyl trimethoxy silane, heating for reaction, filtering, washing and vacuum drying to obtain a modified mica powder intermediate;
SS2 placing the modified mica powder intermediate in N, N-dimethylformamideIn the method, the ultrasonic dispersion is carried out for 0.5 to 1 hour, 2-methyl-2-acrylic acid-2, 6-tetramethyl-4-piperidyl ester and photoinitiator are added, and the ratio of 1.8 to 2.3mw/cm 2 After reacting for 0.5-1h under the irradiation of ultraviolet light, filtering, washing and vacuum drying to obtain the modified mica powder.
7. The high temperature and corrosion resistant PVC material according to claim 6, wherein in step SS1, the temperature is 60-70 ℃ and the time is 1-3h.
8. The high temperature and corrosion resistant PVC material according to claim 6, wherein in step SS2, the photoinitiator is any one of benzoin diethyl ether, benzoin isopropyl ether, benzoin dimethyl ether.
9. The high temperature and corrosion resistant PVC material according to claim 1, wherein the method of making the PVC material comprises the steps of:
adding polyvinyl chloride, modified mica powder, functionalized polycarbonate diol, a dispersing agent, an initiator, a lubricant and a stabilizer in parts by weight into a high-speed mixer, setting the rotating speed of the mixer to be 700-800r/min, heating to 105-110 ℃, stirring for 1-2h, cooling to room temperature, and discharging to obtain a mixture;
and step two, adding the mixture into a double-screw extruder, setting the temperature of the screw extruder to be 160-180 ℃, the screw rotating speed to be 300-500r/min, extruding, cooling and granulating to obtain the high-temperature-resistant corrosion-resistant PVC material.
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